Title:Ab initio Valence Bond Theory with Density Functional
Volume: 3
Issue: 2
Author(s): Chen Zhou, Xun Wu, Peikun Zheng, Fuming Ying, Peifeng Su*Wei Wu*
Affiliation:
- State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and
Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
- State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and
Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
Keywords:
Strongly correlated systems, valence bond theory, density functional theory, multireference, valence bond selfconsistent field, static correlation, dynamic correlation.
Abstract: The accurate description of strongly correlated systems, also known as multireference
systems, requires a balanced treatment of static and dynamic correlations and is an important target
for developing quantum chemical methods. An appealing treatment to economically describe
strongly correlated systems is the multireference density function theory (MRDFT) approach, in
which the static correlation is included in the multiconfigurational wave function, while the density
functional includes the dynamic correlation. This mini-review focuses on the recent progress and
applications of the density functional methods based on valence bond theory. A series of density
functional valence bond (DFVB) methods are surveyed, including the dynamic correlation correction-
based and Hamiltonian matrix correction-based DFVB methods, the hybrid one-parameter
DFVB methods, the block-localized density functional theory and the multistate density functional
theory. These methods have been applied to various chemical and physical property calculations of
strongly correlated systems, including resonance energies, potential energy curves, spectroscopic
constants, atomization energies, spin state energy gaps, excitation energies, and reaction barriers.
Most of the test results show that the density functional methods based on VB theory give comparable
accuracy but require lower computational cost than high-level quantum computational methods
and thus provide a promising strategy for studying strongly correlated systems.
